Modifer, modified and conjugated diene-based polymer and rubber composition including the same

ABSTRACT

The present invention provides a modifier, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer, and more particularly, a modifier which includes a compound represented by Formula 1 and is capable of improving the mixing properties between a conjugated diene-based polymer and a filler, a modified and conjugated diene-based polymer which is modified using the same, and a rubber composition including the modified and conjugated diene-based polymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority based on KoreanPatent Application Nos. 10-2016-0084112, filed on Jul. 4, 2016, and10-2016-0143545, filed on Oct. 31, 2016, the entire contents of whichare incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a modifier used for the modification ofa modified and conjugated diene-based polymer, and more particularly, toa modifier which has excellent affinity with a filler and may improvemixing properties of a conjugated diene-based polymer, a modified andconjugated diene-based polymer which is modified using the same, and arubber composition including the modified and conjugated diene-basedpolymer.

BACKGROUND ART

With the growing concern of energy savings and environmental problemsincreases, the decrease of a fuel consumption ratio of an automobile isbeing required. As a method of fulfill the requirement, a method fordecreasing exothermic properties of tires by using an inorganic fillersuch as silica and carbon black in a rubber composition for formingtires, has been suggested, but dispersion of the inorganic filler in therubber composition was not easy and defects of degrading the physicalproperties of the rubber composition such as abrasion resistance,cracking resistance and processability were rather generated.

In order to solve such defects, a method for modifying a polymerizationactive part of a conjugated diene-based polymer which is obtained byanionic polymerization using an organolithium with a functional groupwhich is capable of interacting with an inorganic filler has beendeveloped as a method for increasing dispersibility of an inorganicfiller such as silica and carbon black in a rubber composition.Particularly, a method for modifying a polymerization active terminal ofa conjugated diene-based polymer using a tin-based compound, a method ofintroducing an amino group, or a modification method using analkoxysilane derivative, etc., has been suggested.

However, if a rubber composition using a modified and conjugateddiene-based polymer which has been modified by the above-describedmethod is prepared, low exothermic properties may be secured, buteffects of improving physical properties of the rubber composition suchas abrasion resistance, processability, or the like are insufficient.

In another method, in a living polymer which is obtained viacoordination polymerization using a catalyst including a lanthanideseries rare earth element compound, a method for modifying a livingactive terminal by a specific coupling agent or a modifier has beendeveloped. However, in a conventionally known catalyst including alanthanide series rare earth element compound, the activity of theliving terminal thus produced is weak, and the modification rate of theterminal is low, and the effects of improving the physical properties ofthe rubber composition is insignificant.

DISCLOSURE OF THE INVENTION Technical Problem

The present invention has been devised in consideration of theabove-mentioned problems, and an object of the present invention is toprovide a modifier which has excellent affinity with a filler and iscapable of improving the mixing properties of a conjugated diene-basedpolymer.

In addition, other objects of the present invention are to provide amodified and conjugated diene-based polymer which is modified by themodifier and has improved mixing properties between a polymer and afiller, and a method for preparing the same.

In addition, other objects of the present invention are to provide arubber composition and a tire including the modified and conjugateddiene-based polymer.

Technical Solution

To solve the above-described tasks, according to an embodiment of thepresent invention, there is provided a modifier including a compoundrepresented by the following Formula 1:

in Formula 1, R¹ to R³ may be each independently a trivalent hydrocarbongroup which is substituted with at least one substituent selected fromthe group consisting of a halogen group, an alkyl group of 1 to 20carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl groupof 6 to 30 carbon atoms, and —R⁶COOR⁷; or an unsubstituted divalenthydrocarbon group of 1 to 10 carbon atoms, where all R¹ to R³ may not bethe trivalent hydrocarbon group; or the divalent hydrocarbon group, atthe same time, R⁴ may be a single bond, an alkylene group of 1 to 20carbon atoms, or a cycloalkylene group of 3 to 20 carbon atoms, R⁵ maybe a silyl group which is unsubstituted or substituted with an alkylgroup of 1 to 20 carbon atoms; halogen; a cyano group; or —COR⁸, R⁶ maybe a single bond, an alkylene group of 1 to 20 carbon atoms, or acycloalkylene group of 3 to 20 carbon atoms, R⁷ may be an alkyl group of1 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms, andR⁸ may be one selected from the group consisting of an alkoxy group of 1to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroarylgroup of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 10carbon atoms, a heteroamine group of 2 to 10 carbon atoms and adisilylamino group of 3 to 10 carbon atoms.

In addition, according to other embodiments of the present invention,there are provided a modified and conjugated diene-based polymerincluding a functional group derived from the modifier, and a method forpreparing the same.

Further, according to other embodiments of the present invention, thereare provided a rubber composition and a tire including the modified andconjugated diene-based polymer.

Advantageous Effects

According to the present invention, a modifier which has excellentaffinity with a filler and is capable of improving mixing properties ofa conjugated diene-based polymer is provided, and further, a modifiedand conjugated diene-based polymer which is modified by the modifier andhas improved mixing properties between a polymer and a filler, a methodfor preparing the same, and a tire including the same, are provided.

BEST NODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail toassist the understanding of the present invention.

It will be understood that words or terms used in the description andclaims of the present invention shall not be interpreted as the meaningdefined in commonly used dictionaries. It will be further understoodthat the words or terms should be interpreted as having a meaning thatis consistent with their meaning of the technical idea of the invention,based on the principle that an inventor may properly define the meaningof the words or terms to best explain the invention.

The modifier according to an embodiment the present invention mayinclude a compound represented by the following Formula 1:

in Formula 1, R¹ to R³ may be each independently a trivalent hydrocarbongroup which is substituted with at least one substituent selected fromthe group consisting of a halogen group, an alkyl group of 1 to 20carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl groupof 6 to 30 carbon atoms, and —R⁶COOR⁷; or an unsubstituted divalenthydrocarbon group of 1 to 10 carbon atoms, where all R¹ to R³ may not bethe trivalent hydrocarbon group; or the divalent hydrocarbon group, atthe same time, R⁴ may be a single bond, an alkylene group of 1 to 20carbon atoms, or a cycloalkylene group of 3 to 20 carbon atoms, R⁵ maybe a silyl group which is unsubstituted or substituted with an alkylgroup of 1 to 20 carbon atoms; halogen; a cyano group; or —COR⁸, R⁶ maybe a single bond, an alkylene group of 1 to 20 carbon atoms, or acycloalkylene group of 3 to 20 carbon atoms, R⁷ may be an alkyl group of1 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbon atoms, andR⁸ may be one selected from the group consisting of an alkoxy group of 1to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroarylgroup of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 10carbon atoms, a heteroamine group of 2 to 10 carbon atoms and adisilylamino group of 3 to 10 carbon atoms.

Unless otherwise defined in the present invention, “trivalenthydrocarbon group which is substituted with a substituent” may mean ahydrocarbon group which is substituted with total trivalence from a bond(divalence) in an N atom-containing ring and a bond (monovalence) withthe defined substituent, or the substituted trivalent hydrocarbon groupmay be a trivalent hydrocarbon group of 1 to 10, or 1 to 5 carbon atomswhich form a ring together with an N atom, excluding the carbon numberof the defined substituent.

In addition, unless otherwise defined in the present invention, “singlebond” may mean a single covalent bond itself, which does not include aseparate atom or molecular group.

In addition, unless otherwise defined in the present invention, “silylgroup unsubstituted or substituted with an alkyl group of 1 to 20 carbonatoms” may mean one selected from the group consisting of anunsubstituted monovalent silyl group and di- to tetra-valent silyl groupsubstituted with the alkyl group.

The modifier according to the present invention may be the compoundrepresented by Formula 1 itself, or may include another compound whichmay modify a conjugated diene-based polymer together with the compoundrepresented by Formula 1.

In addition, the modifier according to the present invention includes acyclized tertiary amine derivative as the compound represented byFormula 1, and in a conjugated diene-based polymer, particularly, aconjugated diene-based polymer having an active organometal part, themodifier may modify the conjugated diene-based polymer by imparting aconjugated diene-based polymer with a functional group via asubstitution or addition reaction with the active organometal part.

Meanwhile, the modifier according to an embodiment of the presentinvention includes a functional group which is capable of improvingaffinity with a filler in a molecule, and mixing properties between apolymer and a filler may be improved. Further, by including a cyclizedtertiary amine derivative as described above, the modifier may preventthe agglomeration between fillers in a rubber composition and mayimprove the dispersibility of a filler. In an embodiment, if silicawhich is a kind of an inorganic filler is used as a filler,agglomeration may be easily arise between hydroxide groups present onthe surface of the silica due to a hydrogen bond, but the cyclizedtertiary amino group may inhibit the hydrogen bond between hydroxidegroups of the silica, thereby improving the dispersibility of thesilica. As described above, the modifier has a structure which maymaximize the mixing properties of a modified and conjugated diene-basedpolymer, and a modified and conjugated diene-based polymer havingexcellent balance of mechanical properties of a rubber composition suchas abrasion resistance and processability may be efficiently prepared.

According to an embodiment of the present invention, in Formula 1, R¹ toR³ may be each independently a trivalent hydrocarbon group which issubstituted with —R⁶COOR⁷; or an unsubstituted divalent hydrocarbongroup of 1 to 10 carbon atoms, where all R¹ to R³ may not be thetrivalent hydrocarbon group; or the divalent hydrocarbon group, at thesame time, R⁴ may be a single bond, or an alkylene group of 1 to 20carbon atoms, R⁵ may be a silyl group which is substituted with an alkylgroup of 1 to 20 carbon atoms; halogen; a cyano group; or —COR⁸, R⁶ maybe a single bond, R⁷ may be an alkyl group of 1 to 20 carbon atoms, andR⁸ may be one selected from the group consisting of an alkoxy group of 1to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroarylgroup of 2 to 30 carbon atoms, a heterocycloalkyl group of 2 to 10carbon atoms, a heteroamine group of 2 to 10 carbon atoms, and adisilylamino group of 3 to 10 carbon atoms.

According to an embodiment of the present invention, the compoundrepresented by Formula 1 may be a compound represented by the followingFormula 2:

in Formula 2, R¹ and R³ may be each independently a trivalenthydrocarbon group which is substituted with at least one substituentselected from the group consisting of a halogen group, an alkyl group of1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, and anaryl group of 6 to 30 carbon atoms; or an unsubstituted divalenthydrocarbon group of 1 to 10 carbon atoms, R² may be a trivalenthydrocarbon group which is substituted with —R⁶COOR⁷, R⁴ and R⁶ may besingle bonds, R⁷ may be an alkyl group of 1 to 20 carbon atoms, or acycloalkyl group of 3 to 20 carbon atoms, and R⁹ to R¹¹ may be eachindependently hydrogen, or an alkyl group of 1 to 20 carbon atoms.

In another embodiment, in Formula 2, R¹ and R³ may be each independentlyan unsubstituted divalent hydrocarbon group of 1 to 10 carbon atoms, Rmay be a trivalent hydrocarbon group which is substituted with —R⁶COOR⁷,R⁴ and R⁶ may be single bonds, R¹¹ may be an alkyl group of 1 to 20carbon atoms, and R⁹ to R¹¹ may be each independently an alkyl group of1 to 20 carbon atoms.

In a particular embodiment, the compound represented by Formula 2 may beone selected from the group consisting of the compounds represented bythe following Formulae 2-1 to 2-3:

The modified and conjugated diene-based polymer according to anembodiment of the present invention may include a functional groupderived from the modifier. Particularly, the modified and conjugateddiene-based polymer may be prepared by modifying a conjugateddiene-based polymer with the modifier.

The conjugated diene-based polymer may be a butadiene homopolymer suchas polybutadiene, or a butadiene copolymer such as a butadiene-isoprenecopolymer.

In a particular embodiment, the conjugated diene-based polymer mayinclude from 80 to 100 wt % of a 1,3-butadiene monomer derived repeatingunit, and selectively 20 wt % or less of other conjugated diene-basedmonomer derived repeating unit which is copolymerizable with1,3-butadiene. Within the ranges, effects of not degrading the contentof 1,4-cis bonds in a polymer may be attained. In this case, the1,3-butadiene monomer may include 1,3-butadiene or the derivativesthereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and2-ethyl-1,3-butadiene, and the other conjugated diene-based monomerwhich is copolymerizable with 1,3-butadiene may include2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, or the like,where one or a compound of at least two thereof may be used.

According to an embodiment of the present invention, the conjugateddiene-based polymer may be a conjugated diene-based polymer including anorganometal part, which is derived from a catalyst composition includinga lanthanide series rare earth element-containing compound, that is,activated from a catalyst, particularly, a neodymium catalyzedbutadiene-based polymer including a 1,3-butadiene monomer derivedrepeating unit.

In the present invention, the activated organometal part of theconjugated diene-based polymer may be an activated organometal part atthe terminal of the conjugated diene-based polymer (activatedorganometal part at the terminal of a molecular chain), an activatedorganometal part in a main chain, or an activated organometal part in aside chain. Among them, in case of obtaining an activated organometalpart of the conjugated diene-based polymer by anionic polymerization orcoordination anionic polymerization, the activated organometal part maybe a terminal activated organometal part.

In addition, the modified and conjugated diene-based polymer accordingto an embodiment of the present invention may have optimized propertiesof molecular weight distribution, mooney viscosity, etc. to improve thebalance of physical properties of a rubber composition, includingviscoelasticity, tensile properties and processability via the controlof the conditions of a catalyst composition, polymerization, etc. duringthe preparation thereof.

Particularly, the modified and conjugated diene-based polymer may havenarrow molecular weight distribution (Mw/Mn) of 2.0 to 3.5. If appliedto a rubber composition within this range, effects of improving tensileproperties and viscoelasticity may be achieved. The molecular weightdistribution may be, for example, from 2.5 to 3.5, from 2.5 to 3.2, orfrom 2.6 to 3.0.

In the present invention, the molecular weight distribution of amodified and conjugated diene-based polymer may be calculated from aratio (Mw/Mn) of a weight average molecular weight (Mw) to a numberaverage molecular weight (Mn). In this case, the number averagemolecular weight (Mn) is a common average of an individual polymermolecular weight, which is obtained by measuring the molecular weightsof n polymer molecules, obtaining the total of the molecular weights anddividing the total by n. The weight average molecular weight (Mw) showsmolecular weight distribution of a polymer composition. All molecularweight average values may be expressed by gram per mol (g/mol). Inaddition, each of the weight average molecular weight and the numberaverage molecular weight may mean a polystyrene converted molecularweight analyzed by gel permeation chromatography (GPC).

The modified and conjugated diene-based polymer according to anembodiment of the present invention may satisfy the above-describedmolecular weight distribution conditions, and at the same time, may havea weight average molecular weight (Mw) of 3×10⁵ to 1.5×10⁶ g/mol, and anumber average molecular weight (Mn) of 1.0×10⁵ to 5.0×10⁵ g/mol. Ifapplied to a rubber composition within the ranges, tensile propertiesmay be excellent and processability may be good, and workability of therubber composition may be improved and mulling and kneading may becomeeasy, thereby achieving excellent mechanical properties and excellentbalance of the physical properties of the rubber composition. The weightaverage molecular weight may be, for example, from 5×10⁵ to 1.2×10⁶g/mol, or from 5×10⁵ to 8×10⁵ g/mol, and the number average molecularweight may be, for example, from 1.5×10⁵ to 3.5×10⁵ g/mol, or from2.0×10⁵ to 2.7×10⁵ g/mol.

More particularly, if the modified and conjugated diene-based polymeraccording to an embodiment of the present invention satisfies theconditions of the molecular weight distribution together with the weightaverage molecular weight (Mw) and the number average molecular weight atthe same time, and when applied to a rubber composition, tensileproperties, viscoelasticity and processability of the rubber compositionmay be excellent, and the balance between the physical properties may beexcellent.

In addition, the modified and conjugated diene-based polymer accordingto an embodiment of the present invention may have mooney viscosity (MV)of 20 to 70 at 100° C. With the mooney viscosity in the range, evenbetter processability may be attained. The mooney viscosity at 100° C.may be, for example, from 40 to 70, from 40 to 65, or from 42 to 55.

In the present invention, the mooney viscosity may be measured by usinga mooney viscometer, for example, MV2000E of Monsanto Co., Ltd. usingLarge Rotor at a rotor speed of 2±0.02 rpm at 100° C. In this case, aspecimen used was stood at room temperature (23±3° C.) for 30 minutes ormore, and 27±3 g of the specimen was collected and put in a die cavity,and then, Platen was operated for measurement.

The modified and conjugated diene-based polymer according to anembodiment of the present invention may be prepared by a preparationmethod including a modification step of reacting a conjugateddiene-based polymer including an organometal part from activated from alanthanide series rare earth element catalyst composition with amodifier including a compound represented by Formula 1.

In a particular embodiment, in order to react the activated organometalpart of the conjugated diene-based polymer with the modifier for thepreparation of the modified and conjugated diene-based polymer, theconjugated diene-based polymer used may preferably have livingproperties or pseudo living properties. Coordination anionicpolymerization may be used as the polymerization reaction of the polymerhaving such living properties.

According to an embodiment of the present invention, the method forpreparing a modified and conjugated diene-based polymer may furtherinclude a step of preparing a conjugated diene-based polymer having anactivated organometal part via polymerization reaction of conjugateddiene-based monomers in a polymerization solvent using a catalystcomposition including a lanthanide series rare earth element-containingcompound prior to the modification step.

In the catalyst composition, the lanthanide series rare earthelement-containing compound may be a compound including one or two ormore elements among the rare earth elements having atomic number of 57to 71 in the periodic table such as neodymium, praseodymium, cerium,lanthanum and gadolinium, particularly, a compound including neodymium.

In another embodiment, the lanthanide series rare earthelement-containing compound may be a salt which is soluble in ahydrocarbon solvent, such as the carboxylate, alkoxide, β-diketonecomplex, phosphate and phosphite of the lanthanide series rare earthelement, particularly, a neodymium-containing carboxylate.

The hydrocarbon solvent may be a saturated aliphatic hydrocarbon of 4 to10 carbon atoms including butane, pentane, hexane, heptane, etc.; asaturated alicyclic hydrocarbon of 5 to 20 carbon atoms includingcyclopentane, cyclohexane, etc.; an aromatic hydrocarbon includingmono-olefins such as 1-butene and 2-butene, benzene, toluene, xylene,etc.; or a halogenated hydrocarbon including methylene chloride,chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane,chlorobenzene, bromobenzene, chlorotoluene, etc.

According to an embodiment of the present invention, the lanthanideseries rare earth element-containing compound may include a neodymiumcompound represented by the following Formula 3:

in Formula 3, R_(a) to R_(c) are each independently hydrogen, or analkyl group of 1 to 12 carbon atoms, where all R_(a) to R_(c) are nothydrogen at the same time.

In a particular embodiment, the neodymium compound may be at least oneselected from the group consisting of Nd(neodecanoate)₃,Nd(2-ethylhexanoate)₃, Nd(2,2-diethyl decanoate)₃, Nd(2,2-dipropyldecanoate)₃, Nd(2,2-dibutyl decanoate)₃, Nd(2,2-dihexyl decanoate)₃,Nd(2,2-dioctyl decanoate)₃, Nd(2-ethyl-2-propyl decanoate)₃,Nd(2-ethyl-2-butyl decanoate)₃, Nd(2-ethyl-2-hexyl decanoate)₃,Nd(2-propyl-2-butyl decanoate), Nd(2-propyl-2-hexyl decanoate)₃,Nd(2-propyl-2-isopropyl decanoate)₃, Nd(2-butyl-2-hexyl decanoate)₃,Nd(2-hexyl-2-octyl decanoate)₃, Nd(2-t-butyl decanoate)₃, Nd(2,2-diethyloctanoate)₃, Nd(2,2-dipropyl octanoate)₃, Nd(2,2-dibutyl octanoate)₃,Nd(2,2-dihexyl octanoate)₃, Nd(2-ethyl-2-propyl octanoate)₃,Nd(2-ethyl-2-hexyl octanoate)₃, Nd(2,2-diethyl nonanoate)₃,Nd(2,2-dipropyl nonanoate)₃, Nd(2,2-dibutyl nonanoate)₃, Nd(2,2-dihexylnonanoate)₃, Nd(2-ethyl-2-propyl nonanoate)₃, and Nd(2-ethyl-2-hexylnonanoate)₃.

In another embodiment, the lanthanide series rare earthelement-containing compound may particularly be a neodymium compound ofFormula 3 wherein R_(a) is a linear or branched alkyl group of 4 to 12carbon atoms, R_(b) and R_(c) are each independently hydrogen or analkyl group of 2 to 8 carbon atoms, where both R_(b) and R_(c) are nothydrogen at the same time, in consideration of excellent solubility in apolymerization solvent without fear of oligomerization, conversion ratiointo a catalyst active species, and consequent improving effects ofcatalyst activity.

In a more particular embodiment, in Formula 3, R_(a) may be a linear orbranched alkyl group of 6 to 8 carbon atoms, R_(b) and R_(c) may be eachindependently hydrogen or an alkyl group of 2 to 6 carbon atoms, whereR_(b) and R_(c) may not be hydrogen at the same time, and particularlyembodiments may include at least one selected from the group consistingof Nd(2,2-diethyl decanoate)₃, Nd(2,2-dipropyl decanoate)₃,Nd(2,2-dibutyl decanoate)₃, Nd(2,2-dihexyl decanoate)₃, Nd(2,2-dioctyldecanoate)₃, Nd(2-ethyl-2-propyl decanoate)₃, Nd(2-ethyl-2-butyldecanoate)₃, Nd(2-ethyl-2-hexyl decanoate)₃, Nd(2-propyl-2-butyldecanoate)₃, Nd(2-propyl-2-hexyl decanoate)₃, Nd(2-propyl-2-isopropyldecanoate)₃, Nd(2-butyl-2-hexyl decanoate)₃, Nd(2-hexyl-2-octyldecanoate)₃, Nd(2-t-butyl decanoate)₃, Nd(2,2-diethyl octanoate)₃,Nd(2,2-dipropyl octanoate)₃, Nd(2,2-dibutyl octanoate)₃, Nd(2,2-dihexyloctanoate)₃, Nd(2-ethyl-2-propyl octanoate)₃, Nd(2-ethyl-2-hexyloctanoate)₃, Nd(2,2-diethyl nonanoate)₃, Nd(2,2-dipropyl nonanoate)₃,Nd(2,2-dibutyl nonanoate)₃, Nd(2,2-dihexyl nonanoate)₃,Nd(2-ethyl-2-propyl nonanoate)₃, and Nd(2-ethyl-2-hexyl nonanoate)₃.Among the compounds, the neodymium compound may be at least one selectedfrom the group consisting of Nd(2,2-diethyl decanoate)₃, Nd(2,2-dipropyldecanoate)₃, Nd(2,2-dibutyl decanoate)₃, Nd(2,2-dihexyl decanoate)₃, andNd(2,2-dioctyl decanoate)₃.

More particularly, in Formula 3, R_(a) may be a linear or branched alkylgroup of 6 to 8 carbon atoms, and R_(b) and R_(c) may be eachindependently an alkyl group of 2 to 6 carbon atoms.

As described above, the neodymium compound represented by Formula 3includes a carboxylate ligand including an alkyl group with variouslengths with 2 or more carbon atoms as a substituent at an α-positionand may induce steric change around a neodymium central metal to blocktangling phenomenon between compounds, thereby achieving the effects ofrestraining oligomerization. In addition, such neodymium compound hashigh solubility with respect to a polymerization solvent and decreasesthe ratio of neodymium which has difficulty in converting into acatalyst active species and is positioned at the central part, therebyachieving the effects of a high conversion ratio into a catalyst activespecies.

In another embodiment, the weight average molecular weight (Mw) of theneodymium compound represented by Formula 3 may be from 600 to 2,000g/mol. With the weight average molecular weight in the range, excellentcatalyst activity may be shown stably.

In addition, the solubility of the lanthanide series rare earthelement-containing compound may be, for example about 4 g or more withrespect to 6 g of a nonpolar solvent at room temperature (25° C.). Inthe present invention, the solubility of the neodymium compound meansthe degree of clear dissolution without turbidity, and such highsolubility may serve excellent catalyst activity.

The lanthanide series rare earth element-containing compound may beused, for example, in an amount of 0.1 to 0.5 mmol, more particularly,0.1 to 0.2 mmol based on 100 g of the conjugated diene-based monomer.Within this range, catalyst activity is high, an appropriate catalystconcentration is obtained, and effects of omitting a deliming processare attained.

The lanthanide series rare earth element-containing compound may beused, for example, as a reactant type with a Lewis base. The reactantimproves the solubility with respect to the solvent of the lanthanideseries rare earth element-containing compound by the Lewis base andgives effects of storing stably for a long time. The Lewis base may beused, for example, in a ratio of 30 mol or less, or 1 to 10 mol based on1 mol of the rare earth element. The Lewis base may be, for example,acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide,thiophene, diphenyl ether, triethylamine, an organophosphorous compound,or monohydric or dihydric alcohol.

The catalyst composition may include, for example, a lanthanide seriesrare earth element-containing compound, an alkylating agent and ahalogen compound.

The alkylating agent may play the role of a co-catalyst as anorganometal compound which may transport a hydrocarbyl group to othermetal, particularly, may be an organometal compound which is soluble ina nonpolar solvent and which contains a metal-carbon bond, such as anorganoaluminum compound, an organomagnesium compound, an organolithiumcompound, etc.

The organoaluminum compound may be, for example, at least one selectedfrom the group consisting of an alkylaluminum such as trimethylaluminum,triethylaluminum, tri-n-propylaluminum, triisopropylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum,tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, andtrioctylaluminum; a dihydrocarbylaluminum hydride such asdiethylaluminum hydride, di-n-propylaluminum hydride,diisopropylaluminum hydride, di-n-butylaluminum hydride,diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride,diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminumhydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride,phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride,phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride,p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride,p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride,p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride,benzylethylaluminum hydride, benzyl-n-propylaluminum hydride,benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride,benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydrogen; anda hydrocarbylaluminum dihydride such as ethylaluminum dihydride,n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminumdihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

The organomagnesium compound may be, for example, an alkylmagnesiumcompound such as diethylmagnesium, di-n-propylmagnesium,diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium,diphenylmagnesium and dibenzylmagnesium.

The organolithium compound may be, for example, an alkyllithium compoundsuch as n-butyllithium.

The alkylating agent may use at least one selected from the groupconsisting of the organoaluminum compounds, the organomagnesiumcompounds and the organolithium compounds, particularly,diisobutylaluminum hydride (DIBAH) which may play the role of amolecular weight controlling agent during performing polymerizationreaction. In another embodiment, the alkylating agent may be used in anamount of 1 to 100 mol, or 3 to 20 mol based on 1 mol of the lanthanideseries rare earth element-containing compound.

The halogen compound may be at least one selected from the groupconsisting of an aluminum halogen compound; an inorganic halogencompound obtained by substituting aluminum in the aluminum halogencompound with boron, silicon, tin or titanium; and an organohalogencompound such as a t-alkylhalogen compound (alkyl of 4 to 20 carbonatoms).

Particular examples of the inorganic halogen compound may be at leastone selected from the group consisting of dimethylaluminum chloride,diethylaluminumchloride (DEAC), dimethylaluminum bromide,diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminumfluoride, methylaluminum dichloride, ethylaluminum dichloride,methylaluminum dibromide, ethylaluminum dibromide, methylaluminumdifluoride, ethylaluminum difluoride, methylaluminum sesquichloride,ethylaluminum sesquichloride, isobutylaluminum sesquichloride,methylmagnesium chloride, methylmagnesium bromide, methylmagnesiumiodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesiumchloride, butylmagnesium bromide, phenylmagnesium chloride,phenylmagnesium bromide, benzylmagnesium chloride, trimethyltinchloride, trimethyltin bromide, triethyltin chloride, triethyltinbromide, di-t-butyltin dichloride, di-t-butyltin dibromide, dibutyltindichloride, dibutyltin dibromide, tributyltin chloride and tributyltinbromide.

In another embodiment, the organohalogen compound may be at least oneselected from the group consisting of t-butyl chloride, t-butyl bromide,allyl chloride, allyl bromide, benzyl chloride, benzyl bromide,chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethylchloride, triphenylmethylbromide, benzylidene chloride, benzylidenebromide, methyltrichlorosilane, phenyltrichlorosilane,dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane,benzoyl chloride, benzoyl bromide, propionyl chloride, propionylbromide, methyl chloroformate and methyl bromoformate.

The halogen compound may be, for example, at least one selected from thegroup consisting of the inorganic halogen compounds and theorganohalogen compounds, and in another embodiment, may be used in anamount of 1 to 20 mol, 1 to 5 mol, or 2 to 3 mol based on 1 mol of thelanthanide series rare earth element-containing compound.

In another embodiment, the alkylating agent and the halogen compound mayinclude a lanthanide series rare earth element-containing compound whichhas been alkylated and chlorinated in advance, and in this case, aconversion ratio may be further improved.

According to an embodiment of the present invention, the catalystcomposition may further include the conjugated diene-based monomer whichis used in the present polymerization reaction.

As described above, if a portion of the conjugated diene-based monomerused in the present polymerization reaction is premixed with thecatalyst composition and is used in a preforming catalyst compositiontype, catalyst activity may be improved, and further, the conjugateddiene-based polymer thus prepared may be stabilized.

In the present invention, the term “preforming” may meanpre-polymerization in a catalyst system due to the addition of butadieneif a catalyst composition, that is, a catalyst system including alanthanide series rare earth element-containing compound, an alkylatingagent and a halogen compound includes diisobutylaluminum hydride(DIBAH), etc., and a small amount of a conjugated diene-based monomersuch as butadiene is added to decrease the possibility of producingdiverse catalyst active species with DIBAH. In addition, the term“premix” may mean a uniformly mixed state of each compound withoutperforming polymerization in a catalyst system.

Particular examples of the conjugated diene monomer may be at least oneselected from the group consisting of 1,3-butadiene, isoprene,1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene and 2,4-hexadiene. The amount of the conjugateddiene-based monomer used for the preparation of the catalyst compositionmay be a portion within the total amount range used of the conjugateddiene-based monomer used for the polymerization reaction, particularly,from 1 to 100 mol, from 10 to 50 mol, or from 20 to 40 mol based on 1mol of the lanthanide series rare earth element-containing compound.

The above-described catalyst composition may be prepared, for example,by injecting the lanthanide series rare earth element-containingcompound, the alkylating agent, the halogen compound, and selectivelythe conjugated diene-based monomer into an organic solvent one by oneand mixing. In this case, the organic solvent may be a nonpolar solventwhich has no reactivity with the constituent components of the catalystcomposition. Particularly, the organic solvent may use at least oneselected from the group consisting of an aliphatic hydrocarbon-basedsolvent such as pentane, hexane, isopentane, heptane, octane, andisooctane; a cycloaliphatic hydrocarbon-based solvent such ascyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, andethylcyclohexane; and an aromatic hydrocarbon-based solvent such asbenzene, toluene, ethylbenzene, and xylene. Particular example of theorganic solvent may include an aliphatic hydrocarbon solvent such ashexane.

According to an embodiment of the present invention, the polymerizationreaction of a conjugated diene-based polymer using the catalystcomposition may be conducted by radical polymerization, particularly,bulk polymerization, solution polymerization, suspension polymerization,or emulsion polymerization, more particularly, solution polymerization.In another embodiment, the polymerization reaction may be conducted byany one of a batch type method or a continuous type method. In aparticular embodiment, the polymerization reaction for preparing theconjugated diene-based polymer may be conducted by injecting aconjugated diene-based monomer to the catalyst composition and reactingin an organic solvent.

In another embodiment, the polymerization reaction for preparing theconjugated diene-based polymer may be conducted in an organic solvent.The organic solvent may be additionally added to the amount used for thepreparation of the catalyst composition, and in this case, the organicsolvent may be the same as that explained above. In addition, in case ofusing the organic solvent, the concentration of the monomer may be from3 to 80 wt %, or from 10 to 30 wt %.

According to an embodiment of the present invention, additives includinga reaction terminator for finishing polymerization reaction, such aspolyoxyethylene glycol phosphate; and an antioxidant such as2,6-di-t-butyl p-cresol may be further used during conductingpolymerization reaction for preparing the conjugated diene-basedpolymer. Besides, additives for facilitating solution polymerization,particularly, a chelating agent, a dispersant, a pH controlling agent, adeoxidizer, or an oxygen scavenger may be selectively further used.

In another embodiment, the polymerization reaction for preparing theconjugated diene-based polymer may be conducted at 20 to 200° C., or 20to 100° C. for 15 minutes to 3 hours, or 30 minutes to 2 hours. Withinthe ranges, the reaction may be easily controlled, the polymerizationreaction rate and efficiency may be excellent, and the content ofcis-1,4 bond of the conjugated diene-based polymer thus prepared may behigh. In addition, the polymerization reaction for preparing theconjugated diene-based polymer may preferably avoid the inclusion of acompound having deactivation function, such as oxygen, water and carbondioxide in a polymerization reaction system to prevent the deactivationof a catalyst composition including a lanthanide series rare earthelement-containing compound and a polymer.

The polymerization reaction for preparing the conjugated diene-basedpolymer may be quenched by adding an isopropanol solution of2,6-di-t-butyl-p-cresol (BHT), etc. to the polymerization reactionsystem. Then, desolvation treatment such as steam stripping fordecreasing the partial pressure of solvents via supplying vapor, or avacuum drying process may be selectively further conducted.

As a result of the polymerization reaction, a conjugated diene-basedpolymer including an organometal part which is activated from a catalystincluding the lanthanide series rare earth element-containing compound,more particularly, a neodymium catalyzed conjugated diene-based polymerincluding a 1,3-butadiene monomer unit is produced, and the conjugateddiene-based polymer thus prepared may have pseudo living properties.

Meanwhile, in the modification step in the preparation of the modifiedand conjugated diene-based polymer according to an embodiment of thepresent invention, the modifier is added in a stoichiometric quantity ormore with respect to the active organometal part of the conjugateddiene-based polymer to the conjugated diene-based polymer which isprepared by the above-described preparation process, to perform thereaction with the activated organometal part which is combined with thepolymer. In this case, the modifier may be used in an amount of 0.1 to20 mol, or 0.5 to 10 mol based on 1 mol of the lanthanide series rareearth element-containing compound used during preparing the conjugateddiene-based polymer having the activated organometal part. Themodification reaction may be, for example, conducted via solutionreaction or solid reaction, particularly, solution reaction. In anotherembodiment, the modification reaction may be conducted by using a batchtype reactor, or by a continuous type using a multi-step continuous typereactor or an in-line blender.

In another embodiment, the modification reaction may be performed in thesame temperature and pressure conditions as those in a commonpolymerization reaction, and particularly, may be performed at atemperature of 20 to 100° C. Within this range, effects of notincreasing the viscosity of the polymer and not deactivating theactivated terminal of the polymer may be achieved.

The preparation method of the modified and conjugated diene-basedpolymer according to an embodiment of the present invention may furtherinclude precipitation and separation processes with respect to themodified and conjugated diene-based polymer thus prepared. Filtering,separating and drying processes with respect to the precipitatedmodified and conjugated diene-based polymer may follow common methods.

As described above, by the preparation method of the modified andconjugated diene-based polymer according to an embodiment of the presentinvention, a modified and conjugated diene-based polymer having narrowmolecular weight distribution and excellent physical properties,particularly, a neodymium catalyzed butadiene-based polymer may beprepared.

The rubber composition according to an embodiment of the presentinvention may include the modified and conjugated diene-based polymer.

In a particular embodiment, the rubber composition may include themodified and conjugated diene-based polymer in an amount of 10 wt % ormore, or 10 to 100 wt %, and within this range, the improving effects ofexcellent abrasion resistance, crack resistance and ozone resistance therubber composition may be achieved.

In another embodiment, the rubber composition may further include arubber component in an amount of 90 wt % or less based on the totalweight of the rubber composition together with the modified andconjugated diene-based polymer. Specifically, the rubber composition mayfurther include the rubber component in an amount of 1 to 900 parts byweight based on 100 parts by weight of the modified and conjugateddiene-based copolymer.

The rubber component may be a natural rubber or a synthetic rubber,particularly, at least one selected from the group consisting of anatural rubber (NR) including cis-1,4-polyisoprene; a modified naturalrubber which is obtained by modifying or purifying a common naturalrubber, such as an epoxidized natural rubber (ENR), a deproteinizednatural rubber (DPNR), and a hydrogenated natural rubber; and asynthetic rubber such as a styrene-butadiene copolymer (SBR), apolybutadiene (BR), a polyisoprene (IR), a butyl rubber (IIR), anethylene-propylene copolymer, a polyisobutylene-co-isoprene, a neoprene,a poly(ethylene-co-propylene), a poly(styrene-co-butadiene), apoly(styrene-co-isoprene), a poly(styrene-co-isoprene-co-butadiene), apoly(isoprene-co-butadiene), a poly(ethylene-co-propylene-co-diene), apolysulfide rubber, an acryl rubber, a urethane rubber, a siliconerubber, an epichlorohydrin rubber, a butyl rubber, a halogenated butylrubber.

In another embodiment, the rubber composition may further include 10parts by weight or more, or 10 to 120 parts by weight of a filler basedon 100 parts by weight of the modified and conjugated diene-basedpolymer.

The filler may particularly be silica, graphite or carbon black.

The silica may be, for example, wet silica (hydrated silicate), drysilica (anhydrous silicate), calcium silicate, aluminum silicate, orcolloid silica. More particularly, the filler may be wet silica whichhas the most significant improving effects of destructioncharacteristics and compatible effects of wet grip characteristics, andin this case, a silane coupling agent may be used together for theimprovement of reinforcing and low exothermic properties. The silanecoupling agent may particularly include, for example, at least oneselected from the group consisting ofbis(3-triethoxysilylpropyl)tetrasulfide,bis(3-triethoxysilylpropyl)trisulfide,bis(3-triethoxysilylpropyl)disulfide,bis(2-triethoxysilylethyl)tetrasulfide,bis(3-trimethoxysilylpropyl)tetrasulfide,bis(2-trimethoxysilylethyl)tetrasulfide,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane,2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane,3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide,3-trimethoxysilylpropylbenzothiazolyltetrasulfide,3-triethoxysilylpropylbenzolyltetrasulfide,3-triethoxysilylpropylmethacrylatemonosulfide,3-trimethoxysilylpropylmethacrylatemonosulfide,bis(3-diethoxymethylsilylpropyl)tetrasulfide,3-mercaptopropyldimethoxymethylsilane,dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, anddimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and moreparticularly, the silane coupling agent may bebis(3-triethoxysilylpropyl)polysulfide or3-trimethoxysilylpropylbenzothiazyltetrasulfide in consideration of theimproving effect of reinforcing properties.

The silane coupling agent may be used in an amount of 1 to 20 parts byweight, or 5 to 15 parts by weight based on 100 parts by weight ofsilica, and within this range, the effects of the coupling agent may besufficiently shown, and the gelation of a rubber component may beprevented.

The carbon black may, for example, have a nitrogen adsorption specificsurface area of 20 to 250 m/g (measured based on N2SA, JIS K6217-2:2001), and within this range, effects of excellent processabilityand reinforcing performance are achieved. In another embodiment, thecarbon black may have a dibutylphthalate oil absorption (DBP) of 80 to200 cc/100 g, and within this range, effects of excellent processabilityand reinforcing performance are achieved.

The filler may include an inorganic filler of at least one metal, metaloxide, or metal hydroxide selected from aluminum, magnesium, titanium,calcium and zirconium. Particular example of the inorganic filler may beat least one selected from the group consisting of γ-alumina, α-alumina,alumina-hydrate (Al₂O₃.H₂0), aluminum hydroxide [Al(OH)₃], aluminumcarbonate [Al₂(CO %)₂], magnesium hydroxide [Mg(OH)₂], magnesium oxide(MgO), magnesium carbonate (MgCO), talc (3MgO.4SiO₂.H₂O), attapulgite(5Mg0.8SiO₂.9H₂O), titanium white (TiO), titanium black, calcium oxide(CaO), calcium hydroxide [Ca(OH)₂], magnesium aluminate (MgO.Al₂O₃),clay (Al₂O₃.2SiO₂), kaoline (Al₂O₃.2Si0₂.2H₂O), calcium silicate(Ca₂.SiO₄, etc.), aluminum calcium silicate (Al₂O₃.CaO.2SiO₂, etc.),calcium magnesium silicate (CaMgSiO₄), calcium carbonate (CaCO₃),zirconium oxide (ZrO₂), zirconium hydroxide [ZrO(OH)₂nH₂O], zirconiumcarbonate [Zr(CO₃)₂] and crystalline alumino silicate. If the carbonblack and the inorganic filler are mixed and used, the mixing weightratio may be 95:5 to 5:95 in consideration of the improving effects ofperformance.

The rubber composition may be, for example, sulfur crosslinkable, and somay further include a vulcanizing agent. The vulcanizing agent may beparticularly a sulfur powder and may be included in an amount of 0.1 to10 parts by weight based on 100 parts by weight of the rubber component.With the amount used in the above range, elasticity and strengthrequired for a vulcanized rubber composition may be secured, and at thesame time, a low fuel consumption ratio may be attained.

The rubber composition may further include various additives used in acommon rubber industry in addition to the above components,particularly, a vulcanization accelerator, a process oil, a plasticizer,an antiaging agent, a scorch preventing agent, a zinc white, stearicacid, a thermosetting resin, or a thermoplastic resin. The vulcanizationaccelerator may particularly include thiazole-based compounds such as2-mercaptobenzothiazole (M), dibenzothiazyldisulfide (DM), andN-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-basedcompounds such as diphenylguanidine (DPG). The vulcanization acceleratormay be included in an amount of 0.1 to 5 parts by weight based on 100parts by weight of the rubber component.

The process oil acts as a softener in a rubber composition and mayparticularly include a paraffin-based, naphthene-based, or aromaticcompound. More particularly, an aromatic process oil may be used inconsideration of tensile strength and abrasion resistance, and anaphthene-based or paraffin-based process oil may be used inconsideration of hysteresis loss and properties at low temperature. Theprocess oil may be included in an amount of 100 parts by weight or lessbased on 100 parts by weight of the rubber component. With theabove-described amount in the range, the deterioration of tensilestrength and low exothermic properties (low fuel consumption ratio) of avulcanized rubber may be prevented.

The antiaging agent may particularly include a condensate of amines andketones at a high temperature, such asN-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, andpoly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ). The antiaging agentmay be used in an amount of 0.1 to 6 parts by weight based on 100 partsby weight of the rubber component.

The rubber composition may be obtained by mulling using a mullingapparatus such as a banbury mixer, a roll, and an internal mixeraccording to a mixing prescription. In addition, a rubber compositionhaving low exothermic properties and excellent abrasion resistance maybe obtained by a vulcanization process after a molding process.

Therefore, the rubber composition may be useful to the manufacture ofeach member of a tire such as a tire tread, an under tread, a side wall,a carcass coating rubber, a belt coating rubber, a bead filler, achafer, and a bead coating rubber, or to the manufacture of rubberproducts in various industries such as a dustproof rubber, a beltconveyor, and a hose.

BEST NODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be explained in particularreferring to embodiments. However, the following embodiments are onlyfor the illustration of the present invention, and the scope of thepresent invention is not limited thereto.

PREPARATION EXAMPLES Preparation Example 1: Catalyst Composition 1

Into a hexane solution under nitrogen conditions, a neodymiumcarboxylate compound was added, and diisobutylaluminum hydride (DIBAH)and diethylaluminum chloride (DEAC) were injected one by one such that amolar ratio of neodymium compound:DIBAH:DEAC=1:9-10:2-3 and mixed toprepare a catalyst composition. The catalyst composition thus preparedwas instantly used or used after storing at −30 to 20° C. under nitrogenconditions.

Preparation Example 2: Catalyst Composition 2

A pre-alkylated neodymium carboxylate compound purchased from COMARChemical Co., Ltd. was used.

Preparation Example 3: Preparation of ethyl 1-(trimethylsilyl)piperidine-4-carboxylate

To a solution of 2 g of ethyl piperidine-4-carboxylate dissolved indichloromethane (CH₂Cl₂), 1.77 ml of triethylamine (Et₃N) and 1.62 ml oftrimethylsilyl chloride (TMSCl) were added at 0° C., and the reactionmixture was stirred for 5 hours at 0° C. Then, solvents in the producedsolution were evaporated under a reduced pressure, and the remainingproduct was re-dissolved in hexane and filtered to obtain a compound ofthe structure below. ¹H nuclear magnetic resonance spectroscopicspectrum was observed.

¹H NMR (500 MHz, CDCl₃) δ 4.11-4.08 (m, 2H), δ 3.13-3.11 (m, 2H), δ2.61-2.54 (m, 2H), δ 2.34-2.32 (m, 1H), δ 1.74 (m, 2H), δ 1.42 (m, 2H),δ 1.23-1.22 (m, 3H), δ 0.05-0.00 (m, 9H).

Preparation Example 4: Preparation of ethyl1-(trimethylsilyl)piperidine-3-carboxylate

To a solution of 2 g of ethyl piperidine-3-carboxylate dissolved indichloromethane (CH₂Cl₂), 1.77 ml of triethylamine (Et₃N) and 1.62 ml oftrimethylsilyl chloride (TMSCl) were added at 0° C., and the reactionmixture was stirred for 3 hours at 0° C. Then, volatile solvents wereremoved under a reduced pressure, and the residue was filtered twiceusing hexane. The filtered crude material was separated via distillationunder a reduced pressure to obtain a compound of the structure below. ¹Hnuclear magnetic resonance spectroscopic spectrum was observed.

¹H NMR (500 MHz, CDCl₃) δ 4.10-4.09 (m, 2H), δ 3.19-3.17 (m, 1H), δ 2.93(m, 1H), δ 2.79-2.72 (m, 1H), δ 2.54 (m, 1H), δ 2.24 (m, 1H), δ1.94-1.92 (m, 1H), δ 1.63-1.58 (m, 2H), δ 1.28-1.21 (m, 4H), δ 0.00 (m,9H).

EXAMPLES Example 1: Preparation of Modified and Conjugated Diene-BasedPolymer

<Preparation of Butadiene Polymer>

To a completely dried reactor, vacuum and nitrogen were alternatelyapplied, and to the reactor in a vacuum state, 4.7 kg of a mixturesolution of 1,3-butadiene/hexane was injected and Catalyst Composition 1of Preparation Example 1 was added. Then, polymerization reaction wasperformed at 60 to 90° C. for 15 to 60 minutes to prepare a butadienepolymer including a terminal activated aluminum part.

<Modification Reaction>

After finishing the polymerization reaction of 1,3-butadiene, a hexanesolution including the modifier (1-10 eq. based on catalyst) prepared inPreparation Example 3 was added to a polybutadiene polymerizationsolution including an aluminum part activated from the catalystcomposition, and then was reacted for 30 to 60 minutes under the sametemperature conditions as the polymerization conditions. Then, a hexanesolution including a polymerization terminator was injected to terminatethe reaction, and a hexane solution including an antioxidant wasinjected to prepare a modified butadiene-based polymer.

Example 2: Preparation of Modified and Conjugated Diene-Based Polymer

A modified and conjugated diene-based polymer was prepared by the samemethod as Example 1 except for using Catalyst Composition 2 ofPreparation Example 2 as a catalyst composition during preparing abutadiene polymer and using the modifier prepared in Preparation Example4 as a modifier during modification reaction.

Comparative Example 1

BR1208 (manufacturer, LG Chem, Ltd.) was used as unmodified Nd—BR.

Comparative Example 2

CB24 (manufacturer, Lanxess Co.) was used as unmodified Nd—BR.

EXPERIMENTAL EXAMPLES Experimental Example 1

For the polymers before modification and the polymers after modificationin Examples 1 and 2, and the polymers of Comparative Examples 1 and 2,modification or unmodification state, a number average molecular weight(Mn), a weight average molecular weight (Mw), molecular weightdistribution (MWD), mooney viscosity (MV) and solution viscosity weremeasured, respectively.

-   -   Number average molecular weight (Mn, ×10⁵ g/mol), weight average        molecular weight (Mw, ×10⁵ g/mol), and molecular weight        distribution (MWD): measured using gel permeation chromatography        for each of the polymers.    -   Mooney viscosity (MV) (ML1+4, @100° C. and −S/R) (MU): measured        by using MV-2000E of Monsanto Co., Ltd. at 100° C. using Large        Rotor at a rotor speed of 2±0.02 rpm. In this case, a specimen        used was stood at room temperature (23±3° C.) for 30 minutes or        more, and 27±3 g of the specimen was collected and put in a die        cavity, and then, Platen was operated and mooney viscosity was        measured while applying torque.

In addition, during measuring the mooney viscosity, the change of themooney viscosity shown with the release of the torque was observed, anda −S/R value was determined from the gradient value thereof.

-   -   Solution viscosity (MU): viscosity of a polymer in 5 wt %        toluene was measured at 20° C.

TABLE 1 Example Comparative Example Division 1 2 1 2 CatalystComposition Prepa- Prepa- — — ration ration Example 1 Example 2 ModifierPrepa- Prepa- — — ration ration Example 3 Example 4 Before Mn 2.66 2.621.57 2.56 modification Mw 6.68 7.77 7.78 6.08 Mw/Mn 2.57 2.96 4.96 2.37ML1 + 4 — — 45 45 −S/R — — 0.7274 0.5997 After Mn 2.49 2.64 — —modification Mw 6.94 7.88 — — Mw/Mn 2.78 2.99 — — ML1 + 4 47 52 — — −S/R0.8215 0.9863 — — Solution 274 341 N/A 151 viscosity

In Table 1, N/A means unmeasurable.

As shown in Table 1, for the cases of Examples 1 and 2, which wereprepared according to the present invention, it was found that themooney viscosity and the weight average molecular weight were increasedand the molecular weight distribution was increased after modification.

Experimental Example 2

With respect to 100 parts by weight of the modifier or unmodifiedconjugated diene-based polymer of Example 1 or 2, or Comparative Example1 or 2, 70 parts by weight of graphite, 22.5 parts by weight of aprocess oil, 2 parts by weight of an antiaging agent (TMDQ), 3 parts byweight of zinc white (ZnO), and 2 parts by weight of stearic acid weremixed to prepare a rubber mixture. To the rubber mixture thus prepared,2 parts by weight of a sulfur powder, 2 parts by weight of avulcanization accelerator (CZ) and 0.5 parts by weight of avulcanization accelerator (DPG) were added, followed by vulcanizing at160° C. for 25 minutes to manufacture a rubber specimen. With respect tothe rubber specimen thus manufactured, tensile properties,viscoelasticity and abrasion resistance were evaluated.

In detail, with respect to the rubber specimen thus manufactured,modulus when elongated by 300% (300% modulus (M-300%), kgf/cm²), tensilestrength (kgf/cm²) of a vulcanized material, and elongation (%) of avulcanized material when broken were measured after vulcanizing at 150°C. for t90 minutes according to ASTM D412. In addition, each measuredvalue was indexed with respect to the measured value of ComparativeExample 2 of 100.

In addition, with respect to the rubber specimen, viscoelasticitycoefficient (tan δ) at 60° C. was measured with a frequency of 10 Hz anda deformation rate of 3%. In addition, each measured value was indexedwith respect to the measured value of Comparative Example 2 of 100.

In addition, with respect to the rubber specimen, DIN abrasion test wasconducted according to ASTM D5963 and DIN wt loss index (loss volumeindex: abrasion resistance index, Method A (ARI_(A))) is shown together.The higher the index is, the better the abrasion resistance is.

TABLE 2 Example Comparative Example Division 1 2 1 2 Modifier Prepa-Prepa- — — ration ration Example 3 Example 4 M-300% 100 98 83 97 M-300%index 104 101 86 100 T/S 184 182 166 177 T/S index 104 103 94 100Elongation 485 491 523 484 Elongation index 100 101 108 100 Tan δ @60°C. 0.138 0.140 — 0.149 Tan δ @60° C. index 108 106 83 100 DIN wt lossindex 106 99 — 100

As shown in Table 2, different from Comparative Example 1 which showsdegraded modulus when elongated by 300%, tensile strength andviscoelasticity except for elongation when compared to ComparativeExample 2, it was found for Examples 1 and 2 in which modification usinga modifier according to the present invention was conducted, that all ofmodulus when elongated by 300%, tensile strength, and tensile propertiesand viscoelasticity of elongation were excellent and further, it wasfound that abrasion resistance was maintained to the same level asComparative Example 2 or improved.

1. A modifier comprising a compound represented by the following Formula1:

in Formula 1, R¹ to R³ are each independently a trivalent hydrocarbongroup which is substituted with at least one substituent selected fromthe group consisting of a halogen group, an alkyl group of 1 to 20carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl groupof 6 to 30 carbon atoms, and —R⁶COOR⁷; or an unsubstituted divalenthydrocarbon group of 1 to 10 carbon atoms, where all R¹ to R³ are notthe trivalent hydrocarbon group; or the divalent hydrocarbon group, atthe same time, R⁴ is a single bond, an alkylene group of 1 to 20 carbonatoms, or a cycloalkylene group of 3 to 20 carbon atoms, R⁵ is a silylgroup which is unsubstituted or substituted with an alkyl group of 1 to20 carbon atoms; halogen; a cyano group; or —COR⁸, R⁶ is a single bond,an alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of 3to 20 carbon atoms, R⁷ is an alkyl group of 1 to 20 carbon atoms, or acycloalkyl group of 3 to 20 carbon atoms, and R⁸ is one selected fromthe group consisting of an alkoxy group of 1 to 10 carbon atoms, an arylgroup of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbonatoms, a heterocycloalkyl group of 2 to 10 carbon atoms, a heteroaminegroup of 2 to 10 carbon atoms, and a disilylamino group of 3 to 10carbon atoms.
 2. The modifier of claim 1, wherein in Formula 1, R¹ to R³are each independently a trivalent hydrocarbon group which issubstituted with —R⁶COOR⁷; or an unsubstituted divalent hydrocarbongroup of 1 to 10 carbon atoms, where all R¹ to R³ are not the trivalenthydrocarbon group; or the divalent hydrocarbon group, at the same time,R⁴ is a single bond, or an alkylene group of 1 to 20 carbon atoms, R⁵ isa silyl group which is substituted with an alkyl group of 1 to 20 carbonatoms; halogen; a cyano group; or —COR⁸, R⁶ is a single bond, R⁷ is analkyl group of 1 to 20 carbon atoms, and R⁸ is one selected from thegroup consisting of an alkoxy group of 1 to 10 carbon atoms, an arylgroup of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbonatoms, a heterocycloalkyl group of 2 to 10 carbon atoms, a heteroaminegroup of 2 to 10 carbon atoms, and a disilylamino group of 3 to 10carbon atoms.
 3. The modifier of claim 1, wherein the compoundrepresented by Formula 1 is a compound represented by the followingFormula 2:

in Formula 2, R¹ and R³ are each independently a trivalent hydrocarbongroup which is substituted with at least one substituent selected fromthe group consisting of a halogen group, an alkyl group of 1 to 20carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, and an arylgroup of 6 to 30 carbon atoms; or an unsubstituted divalent hydrocarbongroup of 1 to 10 carbon atoms, R² is a trivalent hydrocarbon group whichis substituted with —R⁶COOR⁷, R⁴ and R⁶ are single bonds, R⁷ is an alkylgroup of 1 to 20 carbon atoms, or a cycloalkyl group of 3 to 20 carbonatoms, and R⁹ to R¹¹ are each independently hydrogen, or an alkyl groupof 1 to 20 carbon atoms.
 4. The modifier of claim 3, wherein thecompound represented by Formula 2 is one selected from the groupconsisting of the compounds represented by the following Formulae 2-1 to2-3:


5. A modified and conjugated diene-based polymer, comprising afunctional group derived from the modifier according to claim
 1. 6. Themodified and conjugated diene-based polymer of claim 5, wherein themodified and conjugated diene-based polymer has molecular weightdistribution of 2.0 to 3.5.
 7. The modified and conjugated diene-basedpolymer of claim 5, wherein the modified and conjugated diene-basedpolymer has a mooney viscosity (MV) of 20 to 70 at 100° C.
 8. A methodfor preparing a modified and conjugated diene-based polymer, the methodcomprising: a modification step of reacting a conjugated diene-basedpolymer comprising an organometal part activated from a lanthanideseries rare earth element catalyst composition with a modifiercomprising a compound represented by the following Formula 1:

in Formula 1, R¹ to R³ are each independently a trivalent hydrocarbongroup which is substituted with at least one substituent selected fromthe group consisting of a halogen group, an alkyl group of 1 to 20carbon atoms, a cycloalkyl group of 3 to 20 carbon groups, an aryl groupof 6 to 30 carbon atoms, and —R⁶COOR⁷; or an unsubstituted divalenthydrocarbon group of 1 to 10 carbon atoms, where all R¹ to R³ are notthe trivalent hydrocarbon group; or the divalent hydrocarbon group, atthe same time, R⁴ is a single bond, an alkylene group of 1 to 20 carbonatoms, or a cycloalkylene group of 3 to 20 carbon atoms, R⁵ is a silylgroup which is unsubstituted or substituted with an alkyl group of 1 to20 carbon atoms; halogen; a cyano group; or —COR⁸, R⁶ is a single bond,an alkylene group of 1 to 20 carbon atoms, or a cycloalkylene group of 3to 20 carbon atoms, R⁷ is an alkyl group of 1 to 20 carbon atoms, or acycloalkyl group of 3 to 20 carbon atoms, and R⁸ is one selected fromthe group consisting of an alkoxy group of 1 to 10 carbon atoms, an arylgroup of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbonatoms, a heterocycloalkyl group of 2 to 10 carbon atoms, a heteroaminegroup of 2 to 10 carbon atoms, and a disilylamino group of 3 to 10carbon atoms.
 9. The method for preparing a modified and conjugateddiene-based polymer of claim 8, further comprising prior to themodification step, a step of performing polymerization reaction of aconjugated diene-based monomer using a catalyst composition comprising alanthanide series rare earth element-containing compound in apolymerization solvent to prepare a conjugated diene-based polymerhaving an activated organometal part.
 10. The method for preparing amodified and conjugated diene-based polymer of claim 9, wherein thecatalyst composition comprises the lanthanide series rare earthelement-containing compound, an alkylating agent and a halogen compound.11. The method for preparing a modified and conjugated diene-basedpolymer of claim 9, wherein the lanthanide series rare earthelement-containing compound comprises a neodymium compound representedby the following Formula 3:

in Formula 3, R_(a) to R_(c) are each independently hydrogen, or analkyl group of 1 to 12 carbon atoms, where all R_(a) to R_(c) are nothydrogen, at the same time.
 12. The method for preparing a modified andconjugated diene-based polymer of claim 9, wherein the catalystcomposition further comprises a conjugated diene-based monomer.
 13. Themethod for preparing a modified and conjugated diene-based polymer ofclaim 8, wherein the conjugated diene-based polymer comprising theactivated organometal part is a conjugated diene-based polymercomprising a terminal activated organometal part.
 14. The method forpreparing a modified and conjugated diene-based polymer of claim 8,wherein the conjugated diene-based polymer comprising the activatedorganometal part is a neodymium catalyzed butadiene-based polymercomprising a repeating unit derived from an 1,3-butadiene monomer.